JP2009514805A - Method and associated apparatus for converting organic compounds using liquefied metal alloys - Google Patents

Abstract

Organic compounds can be converted by exposure to heat flow through the liquefied metal alloy. Methods and related apparatus for converting organic compounds are provided.

Description

FIELD The present invention relates to methods and apparatus for converting organic compounds, and more particularly to methods and apparatus for converting organic compounds using liquefied metal alloys.

CROSS REFERENCE TO RELATED PATENT APPLICATIONS This application is a U.S. patent application a200509452 filed on 10 October 2005 and published as publication number UA 74,762 C2 on 16 January 2006 (both are incorporated by reference in their entirety) Are incorporated herein by reference). This application is also Ukrainian patent application a200509544 filed on 11 October 2005 and published on 16 January 2006 as publication number UA 74,763 C2, both of which are hereby incorporated by reference in their entirety. Claim priority).

Background Natural gas is a major source of methane. Other methane sources, such as methane present in coal deposits or formed during mining operations, are contemplated for fuel supply. In various petroleum processes, relatively small amounts of methane are produced.

  The natural gas composition at the wellhead fluctuates, but its main hydrocarbon is methane. For example, the amount of methane in natural gas can vary within the range of about 40 to about 95 volume percent. Other components of natural gas include ethane, propane, butane, pentane (and heavier hydrocarbons), hydrogen sulfide, carbon dioxide, helium and nitrogen.

  Natural gas is classified as dry or wet depending on the amount of condensable hydrocarbons contained. Condensable hydrocarbons generally include hydrocarbons having 3 or more carbon atoms, but may include multiple ethanes. Gas regulation is required to change the composition of the wellhead gas, and processing facilities are usually located at or near the production site. Conventional treatment of wellhead natural gas provides a treated natural gas containing at least a large amount of methane.

  Often, large scale use of natural gas requires an elaborate wide area pipeline system. Although liquefaction is also used as a means of transport, the process for liquefying, transporting, and revaporizing natural gas is complex, energy intensive, and requires a wide range of safety measures. Natural gas transport remains a problem in the development of natural gas sources. It would be very beneficial to be able to convert methane (eg natural gas) into a product that can be handled more easily or transported. Furthermore, direct conversion to olefins such as ethylene or propylene is very beneficial to the chemical industry.

  A common method for methane conversion is steam methane reforming carried out in the presence of nickel or other metal-based catalysts at a high temperature of 600 ° C. to 840 ° C. and a high pressure of about 5 to 100 atmospheres. Disadvantages of steam methane reforming include the use of catalysts, (a) high pressures and temperatures that are expensive to produce and (b) require rugged reactors, and low process yields. .

  US Pat. No. 5,093,542 discloses an alternative methane conversion process in which the gas containing methane and a gaseous oxidant is at a temperature in the range of about 700 ° C. to 1200 ° C. In contact with the non-acidic catalyst in the presence of a halogen promoter, substantially in the absence of alkali metals or their compounds. US Pat. No. 4,962,261 is another alternative of methane to higher molecular weight hydrocarbons in the process of using catalysts containing boron, tin and zinc at temperatures in the range of 500-1000 ° C. A conversion method is disclosed.

  US 2004/0120887 (patent document 3), US 2005/0045467 (patent document 4), US 2003/0182862 (patent document 5), US 6,413,491 (patent document 6) and GB 2,265,382 (patent document 7) are other alternatives. A methane conversion process is disclosed.

  There is still a need to develop a low temperature process for converting methane and other organic compounds that does not necessarily require a metal catalyst and does not require the organic compound to be subjected to overpressure.

U.S. Pat.No. 5,093,542 U.S. Pat.No. 4,962,261 US 2004/0120887 US 2005/0045467 US 2003/0182862 US 6,413,491 GB 2,265,382

Overview
According to one embodiment, a method for converting at least one organic compound comprises initiating a second order phase transition in a liquefied metal alloy; and exposing at least one organic compound to the energy of the second order phase transition. And wherein the exposure converts at least one organic compound.

  According to another aspect, a method for converting at least one organic compound comprises passing a heat stream through a liquefied metal alloy; and thereafter exposing the at least one organic compound to the heat stream, the exposure comprising: Including the step of converting at least one organic compound.

  In yet another aspect, the invention comprises a heat source; a liquefied metal alloy in thermal contact with the heat source; a container containing at least one organic compound, wherein the at least one organic compound is in thermal contact with the alloy, and the at least one compound. An apparatus is provided for passing a heat flow from a heat source through an alloy to convert the heat.

  In yet another aspect, the present invention comprises a heat source; a liquefied metal alloy in thermal contact with the heat source; means for passing at least one organic compound, and the heat source for melting the alloy to convert at least one compound An apparatus is provided in which heat flow from is passed through the alloy.

  In yet another aspect, the invention includes passing a heat stream through a liquefied metal alloy and then exposing the at least one organic compound to the heat stream, wherein the exposure generates hydrogen from the at least one organic compound. A method for producing hydrogen is provided.

DETAILED DESCRIPTION Unless otherwise specified, “one (“ a ”)” or “an” (“an”) means one or more.

  The inventor has discovered that heat flow through a molten metal alloy can convert organic compounds.

  The inventor has also discovered that organic compounds can be converted by exposure to the energy of a secondary phase transition initiated in the molten metal alloy.

  In the above method, the organic compound is converted without contacting the organic compound with a metal catalyst, without directly exposing the organic compound to a high temperature exceeding 500 ° C., and without exposing the organic compound to an overpressure exceeding atmospheric pressure. Happens.

Metal Alloy The metal alloy can be a metal alloy having a low melting point. For example, the melting point of the alloy can be less than 200 ° C, such as less than 150 ° C. The melting point can be either the liquidus temperature of the alloy or the solidus temperature of the alloy.

  Metal alloys are metals in the fifth period of the periodic table, e.g., Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te and I, and It can be a metal having an atomic number greater than 79, for example an alloy comprising one or more metals selected from Hg, Tl, Pb and Bi. Preferably, the metal alloy does not contain a radioisotope. Preferably, the metal alloy comprises one or more of the metals of the fifth period of the periodic table and one or more of the metals having an atomic number in the range of 80-83.

  In some embodiments, the metal alloy can include Bi and Sn. In some embodiments, the metal alloy can further include Pb. Examples of such alloys include wood alloys (50% Bi, 13.3% Sn, 26.7% Pb, 10% Cd) having a melting point of about 70 ° C. and rose alloys (50% Bi) having a melting point of about 100 ° C. 25% Sn, 25% Pb). Other alloys including Bi and Sn can also be used.

  The initiation of the second order transition in the metal can include heating at a temperature above the melting point of the alloy. Initiation of the second order transition may further include stirring of the metal alloy.

  Passing the heat flow through the metal alloy may include heating the metal alloy to a temperature above its melting point to a temperature above 60 ° C. In some embodiments, the temperature of the metal alloy can be from about 80 ° C to about 175 ° C. Further, in some cases, the temperature of the alloy may exceed 175 ° C. The temperature of the alloy can be, for example, 300 ° C to 450 ° C or 320 ° C to 400 ° C or 360 ° C to 410 ° C.

Organic Compound The organic compound can be any organic compound. The organic compound can be an organic compound having an unsaturated CH bond. Examples of such organic compounds are hydrocarbons such as alkanes or cycloalkanes.

  Conversion of the organic compound means that one or more products having a different chemical structure from the starting organic compound are formed as a result of exposure to heat flow through the metal alloy. The conversion of the organic compound may be direct or indirect, i.e., the conversion may be a direct or indirect result of exposure of the organic compound to heat flow through the metal alloy. For example, the conversion of hydrocarbons such as alkanes or cycloalkanes can involve decomposition into products containing hydrogen as a direct result of exposure to heat flow through the metal alloy. The product of direct conversion can be used to convert one or more other organic compounds. For example, hydrogen formed by hydrocarbon conversion can be used to convert a substituted nitro compound to a substituted amino compound. Such conversion is an example of indirect conversion.

  In some embodiments, the one or more organic compounds to be converted can be hydrocarbon feedstocks such as feedstock or natural gas. In such a conversion, the exposure of the hydrocarbon material can last for 0.1-50 seconds or 0.2-12 seconds or 2-40 seconds.

  When exposed to heat flow through the metal alloy, the hydrocarbon raw material can be in the liquid phase at temperatures in the range of 80-175 ° C. In some aspects, the hydrocarbon raw material can be fed into the heat flow exposure zone along with a ballast material that can increase the heat and mass transfer of the hydrocarbon raw material. The ballast material can be a metal, ceramic or other inert material that does not react with the hydrocarbon raw material. Preferably, the ballast material does not change the viscosity of the hydrocarbon raw material.

  The product of the hydrocarbon feedstock conversion may have a different molecular weight than the starting hydrocarbon. The product has a lighter fraction, i.e., a lighter molecular weight than the starting raw material, and may include hydrocarbons rich in hydrogen and a heavy fraction, i.e., a hydrocarbon having a higher molecular weight than the starting raw material. In order to separate the light fraction from the heavy fraction, the former can be evaporated and then condensed to a separate volume using a suitable cooling system. Heavy fractions can be removed in liquid form from areas exposed to heat flow.

  Exposure to heat flow through the liquefied metal alloy can be periodic or continuous. Continuous exposure means that the entire amount of organic compound to be converted is supplied continuously, ie without interruption, to the exposure zone to the heat flow through the metal alloy. Cyclic exposure is meant to include at least two exposure periods separated by a non-exposure period, i.e., a period in which the organic compound is not exposed to heat flow through the metal alloy. Periodic exposure can be achieved by interrupting the supply of organic compounds to the area exposed to the heat flow.

Apparatus An apparatus for converting at least one organic compound comprises a heat source; a metal alloy in thermal contact with the heat source; an apparatus for passing at least one organic compound. The apparatus for passing the at least one organic compound can be any container, conduit, or chamber that can expose the organic compound to a heat flow through the metal alloy. For example, a container or conduit having an inlet for supplying one or more organic compounds to be converted and an outlet for removing conversion products. For example, such a container or conduit can be, for example, a tube. In some aspects, the tube may have a spiral shape to maximize exposure of the organic compound to the heat flow.

  In some embodiments, the container can be immersed in the liquefied metal alloy.

  In some embodiments, the organic compound and the metal alloy are not in direct physical contact. For example, the organic compound passing through the container can be separated from the metal alloy by one or more container walls. Such container walls can be made from nonmagnetic metals including copper alloys such as steel, copper or brass. Preferably, the wall does not include a material that is a permanent magnet. The wall thickness can be 0.1-10 mm.

  The container may have any volume depending on the amount of organic compound that it is desired to convert.

  To prevent oxidation, the molten metal alloy in the device can be protected from the surrounding environment. For example, the metal alloy can be sealed from the ambient environment within the device.

The heat source can be any type of heat source. The heat source may have an intensity of at least 30 kW / m ² , preferably at least 35 kW / m ² . In some aspects, the heat source can be a jacket heated by a burner gas. The heat source may also include a resistance heater, a heating lamp, a high frequency heating coil, and the like.

  The heat source can be separated from the alloy by walls, for example. Such a wall material can be, for example, steel. The wall can also include any non-ferromagnetic material. The wall thickness can range from about 0.1 to about 10 mm.

  In some aspects, the apparatus can further comprise a stirrer immersed in the metal alloy. Such a stirrer can be an anchor stirrer or an impeller fitted with a nozzle. In some aspects, the apparatus may further include a cooling system coupled to the container. A cooling system can be used to condense the evaporation fraction of the conversion product.

  The present invention is further illustrated by the following examples, but is not limited to these examples.

Example Conversion of Methane FIG. 1 is a schematic diagram of an apparatus for converting methane to water and carbon. In FIG. 1, the reaction vessel 1 has a steel wall having a volume in the range of 0.5 to 10 liters and a thickness in the range of 0.1 to 10 mm. A spiral tube 2 is placed at the bottom of the reactor 1. The spiral tube 2 can be made of steel. The spiral tube can also be made from any non-ferromagnetic material. Fill reactor 1 with metal alloy 5. The twisted portion of the spiral tube 2 is completely immersed in the metal alloy. The thickness of the metal alloy on the last twisted segment of the spiral tube is preferably 0.04 m or more. Preferably, the reactor 1 is sealed because moisture in ambient air can cause oxidation of the metal alloy 5. The heated gas conduit 3 is disposed outside the reactor 1.

  After the metal alloy 5 is heated to a temperature of 80 to 175 ° C. to melt the alloy, the stirrer 4 disposed under the spiral tube 2 is operated. The stirrer 4 can be an anchor stirrer having a frequency in the range of 60-120 Hz, or an impeller fitted with a nozzle having a frequency in the range of 150-300 Hz.

After the stirrer 4 has been operated in the heated reactor 1 for about 15 minutes, methane is introduced into the spiral tube 2 through the inlet 6. The methane feed rate is selected so that methane can pass through the spiral tube in 0.2-12 seconds. Although the present invention is not limited by any particular theory, it is believed that heating and agitation causes imitation of phase transitions in metal alloys. Phase energy transition to convert the methane into carbon and hydrogen _{(CH 4 -> 2H 2 +} C), which is removed through a tube outlet 7.

Orthonitrotoluene Conversion The apparatus shown in FIG. 1 can also be used to convert orthonitrotoluene to orthoaminotoluene. To carry out this transformation, the metal alloy is heated to a temperature in the range of 80-175 ° C., the metal alloy is stirred for 15 minutes, and then a mixture containing 1.5 moles of methane per mole of orthonitrotoluene is added to the inlet 6 of tube 2. To introduce. The conversion product of the mixture contains, as a mixture, 2 moles of water, 1 mole of orthoaminotoluene and 1 mole of carbon per mole of orthonitrotoluene. While the foregoing relates to particular preferred embodiments, it will be understood that the invention is not so limited. Those skilled in the art will recognize that various modifications can be made to the disclosed embodiments and that such modifications are intended to be included within the scope of the present invention.

  All publications, patent applications and patents cited herein are hereby incorporated by reference in their entirety.

1 is a schematic diagram of one embodiment of an apparatus for converting organic compounds. FIG.

Claims (79)

(A) initiating a secondary phase transition in the molten metal alloy; and
(B) A method for converting at least one organic compound comprising exposing at least one organic compound to energy of a second order phase transition, the method comprising converting at least one organic compound upon exposure.   2. The method of claim 1, wherein the alloy comprises one or more metals selected from metals of the fifth period of the periodic table and non-radioactive elements having an atomic number greater than 79.   3. The method according to claim 2, wherein the alloy is an alloy containing Bi and Sn.   The method of claim 2, wherein the alloy is a wood alloy.   3. The method according to claim 2, wherein the alloy is a rose alloy.   The method of claim 1, wherein the initiating step comprises heating the alloy to a temperature in the range of 80 ° C. to 175 ° C. to melt the alloy.   The method of claim 6, wherein the initiating step further comprises the step of stirring the alloy. The method of claim 1, wherein the initiating step comprises exposing the metal alloy to a heat flow having a strength of at least 35 kW / m ² .   The method of claim 1, wherein the at least one organic compound comprises at least one alkane.   The method of claim 9, wherein the at least one organic compound comprises methane.   11. The method of claim 10, wherein the at least one organic compound further comprises an aromatic nitro compound.   12. The method of claim 11, wherein the aromatic nitro compound is ortho nitrotoluene and the conversion comprises converting the aromatic nitro compound to an aromatic amino compound upon exposure.   2. The method of claim 1, wherein the exposure decomposes at least one organic compound into a product comprising hydrogen.   The method of claim 1, wherein the at least one organic compound and the metal alloy are not in direct physical contact.   15. The method of claim 14, wherein during the exposure, the metal alloy is separated from at least one organic compound by a steel wall having a thickness of 0.1 mm to 10 mm.   The method of claim 1, wherein at least one organic material is not exposed to the metal catalyst.   The method of claim 1, wherein the at least one organic material is not subjected to further pressure.   2. The method of claim 1, wherein the exposure lasts for 0.2-12 seconds.   2. The method of claim 1, wherein the exposure lasts 2-40 seconds.   The method of claim 1, wherein the exposure is performed continuously.   The method of claim 1, wherein the exposure is performed periodically. A method of converting at least one organic compound comprising: passing a heat stream through a molten metal alloy; and then exposing the at least one organic compound to the heat stream to convert at least one organic compound.   23. The method of claim 22, wherein the metal alloy comprises one or more metals selected from metals of the fifth period of the periodic table and non-radioactive elements having an atomic number greater than 79.   24. The method of claim 23, wherein the alloy is an alloy comprising Bi and Sn.   25. The method of claim 24, wherein the metal alloy is a wood alloy.   25. The method of claim 24, wherein the metal alloy is a rose alloy. Heat flow has a starting intensity of at least 35 kW / m ^2, The method of claim 22.   24. The method of claim 22, wherein the at least one organic compound comprises at least one alkane.   30. The method of claim 28, wherein the at least one organic compound comprises methane.   30. The method of claim 29, wherein the at least one organic compound further comprises an aromatic nitro compound.   32. The method of claim 30, wherein the aromatic nitro compound is orthonitrotoluene and upon exposure, the aromatic nitro compound is converted to an aromatic amino compound.   24. The method of claim 22, wherein the at least one organic compound is decomposed in the product comprising hydrogen by exposing the at least one organic compound.   24. The method of claim 22, wherein the at least one organic compound and the metal alloy are not in direct physical contact.   34. The method of claim 33, wherein the alloy is separated from at least one organic compound by a steel wall having a thickness of 0.1 mm to 10 mm.   24. The method of claim 22, wherein at least one or more organic materials are not exposed to the metal catalyst.   24. The method of claim 22, wherein at least one is not subjected to further pressure.   24. The method of claim 22, wherein the exposure is performed continuously.   24. The method of claim 22, wherein the exposure is performed periodically. Heat source;
A low melting point metal alloy in thermal contact with a heat source; and a container adapted to supply at least one organic compound;
An apparatus wherein, in use, at least one organic compound is in thermal contact with the alloy and a heat flow from a heat source passes through the alloy to convert the at least one organic compound.   40. The apparatus of claim 39, wherein the alloy comprises one or more metals selected from metals of the fifth period of the periodic table and non-radioactive elements having an atomic number greater than 79.   41. The apparatus of claim 40, wherein the alloy is an alloy comprising Bi and Sn.   41. The apparatus of claim 40, wherein the metal alloy is a wood alloy.   41. The apparatus of claim 40, wherein the metal alloy is a rose alloy. During operation the heat source has at least intensity of 35 kW / m ^2, apparatus according to claim 39.   40. The apparatus of claim 39, wherein the alloy and at least one organic compound are not in direct physical contact.   46. The apparatus of claim 45, wherein the alloy and the at least one organic material are separated by a wall having a thickness of 0.1 mm to 10 mm.   46. The apparatus of claim 45, wherein the wall is a steel wall.   40. The apparatus of claim 39, wherein the container is a tube immersed in the alloy.   41. The apparatus of claim 40, wherein the tube is a spiral tube.   40. The apparatus of claim 39, further comprising a stirrer immersed in the alloy.   51. The apparatus of claim 50, wherein the agitator is an anchor stirrer or impeller.   40. The apparatus of claim 39, wherein the alloy is sealed from the ambient environment within the container. Heat source;
A metal alloy that is in thermal contact with a heat source and is in operation a molten metal alloy; and means for exposing at least one organic compound to a heat flow from the heat source, wherein the heat flow is for converting at least one organic compound Passing the molten alloy through the equipment.   54. The apparatus of claim 53, wherein the alloy comprises one or more metals selected from metals of the fifth period of the periodic table and non-radioactive elements having an atomic number greater than 79.   55. The apparatus of claim 54, wherein the alloy is an alloy comprising Bi and Sn.   56. The apparatus of claim 55, wherein the alloy is a wood alloy.   56. The apparatus of claim 55, wherein the alloy is a rose alloy. During operation, the heat source has at least intensity of 35 kW / m ^2, apparatus according to claim 53, wherein.   54. The apparatus of claim 53, wherein the alloy and the at least one organic material are not in direct physical contact.   60. The apparatus of claim 59, wherein the alloy and the at least one organic material are separated by a wall having a thickness of 0.1 mm to 10 mm.   61. The apparatus of claim 60, wherein the wall is a steel wall.   54. The apparatus of claim 53, further comprising a stirrer immersed in the alloy.   63. Apparatus according to claim 62, wherein the agitator is an anchor stirrer or impeller. Passing the heat flow through the molten metal alloy, and then
A method of producing hydrogen, comprising exposing at least one organic compound to a heat flow, wherein the exposure generates hydrogen from the at least one organic compound.   65. The method of claim 64, wherein the alloy comprises one or more metals selected from metals of the fifth period of the periodic table and non-radioactive elements having an atomic number greater than 79.   66. The method of claim 65, wherein the alloy is an alloy comprising Bi and Sn.   68. The method of claim 66, wherein the alloy is a wood alloy.   68. The method of claim 66, wherein the alloy is a rose alloy. Heat flow has at least intensity of 35 kW / m ^2, The method of claim 64, wherein.   65. The method of claim 64, wherein the at least one organic compound comprises at least one alkane.   72. The method of claim 70, wherein the at least one organic compound comprises methane.   65. The method of claim 64, wherein the at least one organic compound and the metal alloy are not in direct physical contact.   73. The method of claim 72, wherein during the exposure, the composite material is separated from at least one organic compound by a steel wall having a thickness of 0.1 mm to 10 mm.   65. The method of claim 64, wherein at least one organic material is not exposed to the metal catalyst.   65. The method of claim 64, wherein the at least one organic material is not subjected to further pressure.   65. The method of claim 64, wherein the exposure lasts for 0.2-12 seconds.   65. The method of claim 64, wherein the exposure lasts 2-40 seconds.   65. The method of claim 64, wherein the exposure is performed continuously.   65. The method of claim 64, wherein the exposure is performed periodically.

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